Disulfonamides of diamino diphenyl sulfones

ABSTRACT

WHEREIN R, R&#39;&#39; , R1 and R1&#39;&#39; are C1 to C20 hydrocarbon radicals. These compounds are useful as initiators or activators in the anionic polymerization of lactam monomers.   D R A W I N G Compounds of the structure

United States Patent 1 Matzner et al.

1 51 Feb. 27, 1973 DISULFONAMIDES OF DIAMINO DIPHENYL SULFONES ville,all of NJ.

[73] Assignee: Union Carbide Corporation, New

York, N.Y.

[22] Filed: April 6, 1970 [21] Appl. No.: 26,045

[52] US. Cl. ..260/397.6, 260/78 L [51] Int. Cl ..C07c 143/74 [58] Fieldof Search ..260/397.6

[56] References Cited OTHER PUBLICATIONS JACS, Vol. 67: 1979, 1980,1983, 1984, 1988 (1945) Heymann et a].

Primary Examiner.lohn D. Randolph Assistant Examiner-S. D. WintersAtt0rneyPaul A. Rose, Aldo J. Cozzi, Gerald R. O- Brien, Jr. and JamesJ. O'Connell 5 7 ABSTRACT Compounds of the structure wherein R, R R andR, are C to C hydrocarbon radicals. These compounds are useful asinitiators or activators in the anionic polymerization of lactammonomers.

4 Claims, No Drawings BACKGROUND OF THE INVENTION 1. Field of theInvention The invention relates to novel disulfonamide derivatives of N,N substituted diamine diphenyl sulfones.

2. Description of the Prior Art Certain diamino diphenyl sulfonederivatives, including certain diamides, have been prepared as disclosedin the Journal of the American Chemical Society, Volume 67, pages 1979to 1990 (1945). The thus disclosed compounds were evaluated forbiological activity.

Although the S group which links the phenyl radicals in this type ofsulfone compound also tends to activate the entire compound for varioustypes of chemical reactions, it has been found that the diaminecompounds, as well as the bis(acetamide) and his (benzamide) derivativesof the diamine compounds are not active enough to be used as initiatorsin the anionic polymerization of lactam monomers.

Attempts to use acetanilide as an initiator for the anionicpolymerization of ecaprolactam were also unsuccessful, Am. Chem. Soc.,Div. Polym. Chem., Preprints 9 l at page 394, (1968).

SUMMARY OF THE INVENTION Certain disulfonamide derivatives of N, Nsubstituted diamino diphenyl sulfone compounds are provided as novelcompounds which are useful as initiators in the anionic polymerizationof lactam monomers.

An object of the present invention is to provide for a novel class ofderivatives of diamine diphenyl sulfone compounds.

A further object of the present invention is to provide compounds whichmay be useful as initiators or activators in the anionic polymerizationof the lactam monomers.

DESCRIPTION OF THE PREFERRED EMBODIMENT The novel compounds of thepresent invention have the structure wherein R, R, R, and R, are thesame or different C, to C inclusive, hydrocarbon radicals.

The R, R, R, and R, radicals may be saturated or unsaturated. Suchradicals would include aliphatic, alicyclic and aromatic radicals suchas methyl, ethyl, propyl, butyl, cycloheptyl, cyclohexyl, allyl,propeneyl, hexadienyl, octadienyl, phenyl, benzyl and naphthyl radicals.

The R, R, R, and R, radicals may also be substituted with one or moreinert substituent radicals. The inert substituent radicals are thosewhich are capable of being substituted on the R, R, R, and R,hydrocarbon radicals and which are inert to the components of thereaction systems in which the novel compounds of the present inventionare formed, as well as to the basic components of the lactampolymerization systems in which they may be employed, i.e., the lactammonomer and the anionic polymerization catalyst.

The preferred R, R, R, and R, radicals are methyl, ethyl, propyl, phenyland naphthyl radicals.

PREPARATION OF THE NOVEL COMPOUNDS The novel compounds of the presentinvention are prepared by reacting a diamine compound having thestructure wherein R and R are as defined above, with one or moresulfonyl compound having the structure (R,S0:\-X or R'|s0 X' wherein R,and R, are as defined above, and X and X are the same or differentradicals and are OH or halogen radicals, to form the desireddisulfonamide compounds, with water or halogen acid being formed as aby-product, depending on whether X and X are OH or halogen,respectively.

The preferred sulfonyl compounds for the purposes of the presentinvention are the sulfonyl halides, notably the sulfonyl chlorides. Atleast 2 moles of the sulfonyl halide are used per mole of the diaminecompound. When the sulfonyl halides are used as the sulfonyl compoundsthe reaction is preferably conducted in a halogen acid accepting solventsuch as pyridine, alkyl substituted pyridines and triethylamine. Atleast 1 mole of the solvent is used per mole of halogen acid formed inthe reaction. Excess solvent may be used for diluent purposes, I

When water is a by-product, the reaction system preferably containsmechanical or chemical means for effectively removing the water so thatthe reaction may be driven to completion.

The use of different sulfonyl compounds which contain different R, andR, radicals could result in the preparation of disulfonamides havingunsymmetrical structures.

The reaction is conducted at atmospheric pressure and at temperatures ofabout to 200 C. The preferred temperature is the reflux temperature ofthe mixture of the components of the reaction system. The reaction maybe run under an inert blanket of a moisture free gas such as nitrogen.The reaction is usually conducted for a period of up to about 24 hours.

The disulfonamide compounds of the present invention are crystallinematerials which may be readily recovered fromthe reaction systems inwhich they are prepared by precipatation with water or by extractionwith solvents such as chloroform followed by crystallization fromappropriate solvents such as chloroform, aqueous ethanol or aqueousacetone.

The following examples are merely illustrative of the present inventionand are not intended as a limitation upon the scope thereof.

EXAMPLE 1 Preparation of N, N-dimethylsulfonyl-N,N'-dimethyl-4,4'-diamino diphenyl sulfone, i.e.,

A solution of 33 g. (0.4 mole) of methanesulfonyl chloride in 50 ml. ofpyridine was added dropwise to a solution of 27.6 grams (0.1 mole) ofbis(N-methyl-paminophenyl)sulfone in 100 ml of pyridine over a period ofabout minutes. After the mild exotherm subsided, the mixture was heatedat reflux for 22 hours. The reaction mixture was poured into water andthe precipitated product was washed with water and recrystallized fromchloroform. There was obtained 24.5 g. of the desired sulfonamide whichhad a melting point of2l3-2l5 C.

Anal: Calc. for C l-i N O s z C, 44.43; H, 4.60; N,

6.48; S, 22.23 Found :C,43.92;H,4.37;N,6.34;S,22.38.

EXAMPLE 2 Polymerization of s-caprolactam using the diamide compoundprepared as in Example 1 as an anionic polymerization initiator.

Into each of two 25 X 200 mm test tubes was added 28.3 g. (0.25 mole) ofmolten caprolactam, and both were then heated at a polymerizationtemperature of 160 C. Two mol percent of a catalyst, sodium hydride, inthe form of a dispersion (57 percent) in oil was added to one of thesetest tubes, while 1.0 mol percent wherein R, R, R and R' are the same ordifferent C, to C inclusive, aliphatic and alicyclic hydrocarbonradicals.

2. A compound as in claim 1 wherein R R and R R 3. A compound as inclaim 1 wherein R R =CH 4. A compound as in claim 3 which isN,N'-dimethyl sulfonyl-N,N'-dimethyl-4,4'-diamino diphenyl sulfone.

l i t i

2. A compound as in claim 1 wherein R R'' and R1 R''1.
 3. A compound asin claim 1 wherein R R'' CH3.
 4. A compound as in claim 3 which isN,N''-dimethyl sulfonyl-N, N''-dimethyl-4,4''-diamino diphenyl sulfone.